Water soluble triazine azo dyestuffs



United States Patent Ofifice 2,891,941" Patented June 23, 1959 Thisinvention. provides valuable new azo-dyestuffs, which contain at leasttwo strongly acid groups imparting solubility in water and. alsozamonohalogen-tnazme radical of the formula (IJ/ (|JHalogen N'\ t Ywhich-is bound to the dyestufi' molecule through an amino bridge of theformula n-l hPl in. which n. is a positive Whole number, and Yrepresents an etherified hydroxyl group.

Especially valuable among the dyestuifs of the above formula aremetal-free dyestufis of the formulain which D represents the radical ofa diazo-component which may contain an azo-linkage, and A represents theradical of a coupling component, and in which one of the radicals A andD, which together contain at least two strongly acid groups impartingsolubility in water, contains bound thereto through an NH-- group atriazine radical of the formula N -o a r 51 inwhich Y represents a loweralkoxy group, and benzyloxy group. or-a phenoxy group which may containa carboxylic acid or sulfonicacid' group.

The aforesaidv amino bridge linking the characteristic grouping oftheFormul'a 1. to the dyestufimolecule may be connected directly orthrough a bridge member, for example, through an alkylene radical orthrough an -SO group, to the radical of the coupling component oradvantageously to the radical'D- of a diazo-component, which isadvantageously at most bicyclic and is of the benzene series.Accordingly, the said radical may be a substituted or. unsubstitutedphenyl radical or a radical ofhigher molecular weight, for example, abicyclic or naphthalene radical which may contain an azo linkage.

The dyestuffs ofthis invention contain, in addition to a'triazinesubstituent' of the Formula 1, at least two strongly acid groupsimparting solubility in Water, such as carboxylic acid or preferablysulfonic acid groups. Advantageously the dyestuffs contain more than onesuch group per azo linkage, that is to say, at least two such groups ina monoazo-dyestuif and at least three such groups in a disazo-dyestufi.These groups imparting solubility in water may be distributed in anydesired man ner in the dyestufi molecule.

The dyestuffs of this invention can be made by replacing in atrihalogen-triazine, especially in cyanuric chloride(2:4:6-trichloro-1:325-triazine), two halogen atoms by reacting one withan amino-azo-dyestufi, which contains at least two acid groups impartingsolubility in water and an acylatable amino group and the other with anorganic hydroxy-compound, for example, benzyl alcohol or cyclohexylalcohol, or a lower aliphatic alcohol or a phenol.

As amino-azo-dyestufis, which contain at least two groups impartingsolubility in water and an acylatable amino group, there may be usedthose'which contain the acylatable amino group in the radical of thecoupling component and/ or advantageously in the radical of thediazo-component.

For making dyestuffs which contain the acylatable amino group in theradical of the coupling component, there may be used for example,coupling components of the benzene or naphthalene series, which owetheir capacity for coupling to the presence of an at most secondaryamino group or an aromatically bound hydroxyl group, or keto-methylenecompounds which contain, in addition to a methylene group capable ofcoupling in a position vicinal to an enolizable keto group, anadvantageously aromatically bound acylatable amino group. As suchcoupling components there may be. mentioned, for example,w-methane-sulfonic acid derivatives of aniline, of ortho-methoxy-anilineand of ortho-carboxyaminobenzene (the w-methane sulfonic acidgroupbeingsplit oif hydrolytically after reduction of the dyestufi to liberate theamino group), and also meta-toluidine, 3 acetylamino 1 aminobenzene,S-ureido l aminobenzene, l aminobenzene 2. methyl 5 methoxy benzene,l-amino'-2:5-dimethoxyor -diethoxy-benzene-, 1 amino- 3 methoxybenzene,1 amino 2' methoxybenzene-5-isopropylbenzene, uor fl-naphthylamine andabove all naphthylamine mono'sulfonic acids, such as1-arninonaphthalene-6-- or -7-sulfo'nic acid,Z-aminO-naphthalene-6sulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, Z-N-methylamino-8-hydroxynaphthalene-6- sulfonic acid,2-alkylaminoor 2-arylamino-5-hydroxy naphthalene-7-sulfonic acid,Z-amino-S-hydroxynaphthalene-7-sulfonic acid, 2-(4'-aminobenzoylamino)-5' hydroxynaphthalene-7-sulfonic acid, 2-(4-aminopheny1'-amino)-5-hydroXnaphthalene-7-sulfonic acid, and also B-keto-carboxylicacidderivatives, especially acetoacetic acid arylides, and above allpyrazolones, such as. lb'enzoylacetamino-3- or-4-(4-aminobenzoyl)-aminobenzene; l acetoacetylamino 4 aminobenzene 3carboxylic acid, 1-acetoacetylamino-3-aminobenzene-4-sulfonic' acid, 1acetocetylamino 4 aminobenzene 3 sulfonic acid,1-acetacetylamino-4-aminobenzene, and also acetoacetyldiaminobenzenes,which may be substituted in the ben: zene nucleus by an alkyl or alkoxygroup or a halogen atom, l-acetoacetylamino-4'-aminodiphenylmonoordisulfonic acid, 1-acetoacetylamino-4-arniuostilbene-Z:2' disulfonicacid and monoacetoacetyl compounds of 1:4- di-aminodiphenyl-urea or ofdiamino-azobenzenesulfonic acids, and also S-pyrazolones such as 1-(3-or 4'-amino)'- phenyl-3-methyl-5-pyrazolone and the corresponding.sulfonic acids, 1-[4'-(4"-aminophenyl)-phenyl]-3-methyl-5 pyrazolone andthe corresponding sulfonic acids, l-[4'- (4" aminophenyl) phenyl] 3methyl -'5 pyraz olone and1-[4-(4"-aminophenyl)-phenyl]-5-pyrazolone-3-carboxylic acid and thecorresponding sulfonic acids, and also the compound of the formula -C-on=on NH, 7

210 H no 9 and finally compounds obtainable by the nitrobenzoylation andreduction of these l-aminoaryl--pyrazolones, which compounds contain anamino group capable of condensing and which are capable of coupling inthe 4-position of the pyrazolone nucleus.

' The diazo-components to be coupled with these coupling components maycontain substituents not imparting solubility in Water, and if desired,azo linkages, and they must contain strongly acid substituents capableof imparting solubility in water, such as sulfonic acid groups, if thecoupling components used as starting materials contain only one orcontain no such groups. These diazo-components may be relatively simplecompounds, for example, aminobenzene sulfonic acids, aminonaphthalenesulfonic acids, amino-pyrene sulfonic acids or aminochrysene sulfonicacids or aminonaphthol sulfonic acids or aminophenol sulfonic acids, orthey may be more complex diazotizable compounds, which contain forexample, one or two azo linkages.

As examples of amines, whose diazo-compounds are coupled with thecoupling components containing the afore said acylatable amino groups,there may be mentioned the following aminosulfonic acids:

or -4 6-disulfonic Dehydrothiotoluidine monoor di-sulfonic acid, etc.There may also be used as diazo-componcnts amino-adyestuffs such asthose obtainable by coupling one of the above-mentioned couplingcomponents containing -NH groups, with the diazo-compounds of theabovementioned amino-sulfonic acids.

For producing starting materials which contain the acylatable aminogroup in the diazo-component, there may be used, for example,diazo-compounds of monoacyl-derivatives of aromatic diamines, forexample, monoacyl-derivatives of 4:4'-diamino-diphenyl-3-sulfonic acid,4:4'-diarninostilbene-2:2-disulfonic acid,4-(4-aminobenzoylamino)-l-aminobenzene-2-sulfonic acid, 1:3- or1:fl-d1aminobenzene, 1:4-diaminobenzene 2 carboxylic ac d,1:3-diaminobenzene-4-sulfonic acid or l:4-diaminobenzene-3-sulfonicacid, Z-methoxy-l:4-diaminobenzene- S-sulfonic acid, the acyl radicalsof which are saponified after coupling to liberate the amino group. Ascoupling components there may be used in this case compounds capable ofcoupling which are free from acylatable amino groups, for example,

B-Keto-carboxylic acid esters or amides which are capable of coupling inthe a-position, for example, acetoacetic acid arylides, pyrazolones,especially S-pyrazolones capable of coupling in the 4-position, such as3-methyl- S-pyrazolone, l-phenyl-3-methyl-5-pyrazolone, l-phenyl-3-methyl-5-pyrazolone-2'- or -3'- or -4'-sulfonic acid, 1-phenyl-S-pyrazolone-3-carboxylic acid, 5-pyraZolone-3- carboxylic acidamide, barbituric acids, hydroxyquinolines or phenols, such asS-hydroxyquinoline, 2:4-dihydroxyquinoline, paracresol,Z-carboxy-l-hydroxybenzene, naphthols such as zxor fi-naphthols, aorB-naphthylamine, 2- nydroxynaphthalene-sulfonic acid amides, andespecially aminoand/ or hydroxy-naphthalene sulfonic acids or theirN-alkyl-, N-arylor N-acylderivatives, such as l-hydroxynaphthalene-Iior-4- or -5- or -8-sulfonic acid, 2-hydroxynaphthalene-4- or -5- or -6- or-7- or 8-su1fonic acid, 1:8-dihydroxynaphthalene-3z-disulfonic acid, 2-hydroxynaphthalene-3z6- or -6:8-disulfonic acid,l-hydroxynaphthalene-3z6- or 3:8-disulfonic acid,2-aminonaphthalene-6-sulfonic acid, 1-an1ino-8-hydroxynaphthalene-2z4-or -3:6- or 4:6-disulfonic acid and the N-acylderivatives ofaminonaphthol sulfonic acids, which contain as the acyl radical, forexample, an acetyl, propionyl, butyryl, chloracetyl, fi-chloropropionyl,benzoyl, ortho-, metaor para-chlorobenzoyl, nitrobenzoyl, tertiarybutylbenzoyl, 3'- or 4'-aminobenzoyl, methaneor ethane-sulfonyl,para-toluene-sulfonyl or chlorobenzene sulfonyl group, or a carbomethoxyor carbethoxy group, or an acyl radical derived from a cyanuric acid,for example, a radical of the formula in which the two substituents Yrepresent halogen atoms or amino groups, and especially substitutedamino groups.

There may also be used as coupling components 5:5-dihydroxy-2'-dinaphthyl-urea-7:7'-sulfonic acid and 5:5- dihydroxy 2:2dinaphthylamine 7:7-disulfonic acid, which like1-amino-2-hydroxynaphthalene-3:6-disulfonic acid can be coupled twicewith the aforesaid diazo-components, and also compounds capable ofcoupling which contain azo-linkages, for example, monoazo-compounds,which can be made, for example, by coupling in an acid medium a simplediazo-compound of the benzene or naphthalene series (for example, adiazotized naphthylamine, an aniline such as chloraniline ornitroaniline, a toluidine, a Z-aminobcnzoic acid, a 5-nitr0-2-aminobenzoic acid or a nitro-aminophenol, or a chloroaminophenol etc.)with 2-amino-S-hydroxynaphthalene- 7-sulfonic acid or with1-hydroxy-8-aminonaphthalene- 3:6-disulfonic acid.

In this case also only those starting materials should be coupledtogether, which lead to the formation of amino-azo-dyestufis containingat least two groups imparting solubility in water.

The condensation of the amino-azo-dyestufis obtained from thesecomponents with cyannric chloride is carried out in such manner that twoexchangeable halogen atoms remain in the condensation product obtained,and of which halogen atoms one is exchanged forthe radical of an organichydroxy-cornpound. As such hydroxy-compounds there may be used aliphaticor aromatic hydroxycompounds, such as methyl alcohol, ethyl alcohol,isopropyl alcohol, butyl alcohol, cyclohexanol, methoxyethyl alcohol, orphenols free from sulfonic acid groups, such as phenol, ortho-, metaorpara-cresol, 4-secondary butylphenols or especially l-hydroxybenzene-2-or -3- or -4-sulfonic acid or salicylic acid, and also heterocyclic oraraliphatic alcohols, such as furyl alcohol or benzyl alcohol. Goodresults are generally obtained with the correspond ing alkali metalalcoholates or phenolates.

The condensation of these alcohols or phenols or their alkali metalcompounds with the dihalogentuiazine dyestufls in the process of thisinvention is advantageously carried out in the presence of anacid-binding agent, such as sodium acetate or sodium carbonate and underconditions such that an exchangeable halogen atom remains in theproduct, that is to say, for example, in an organic solvent or at arelatively low temperature in an aqueous medium.

Instead of condensing the cyanuric chloride first with the aminoazo-dyestuff and then with the alcohol, the procedure may be reversed byfirst condensing an alcohol or a phenol with cyanuric chloride to form adihalogentriazine of the formula Y(l (ll-Halogen l'alogen in which Y hasthe meaning given in connection with Formula 1, and subsequentlycondensing the primary condensation product of the Formula 3 with theamino-a20- dyestutf, which contains at least two strongly acid groupsimparting solubility in water and also an acylatable amino group, forexample, with an amino-azo-dyestufi obtainable from the componentsmentioned above.

The dyestuffs of this invention can also be made by a modification ofthe above process. In this modification of the process the aforesaidmonohalogentriazine radical is not incorporated into the finisheddyestuffs or into the components used for making them. Thus, a dihalogentn'azine of the Formula 3 may be condensed with a coupling component ordiazo component suitable for making the dyestuif by coupling andcontaining, in addition to the group capable of leading to dyestuflformation, an acylatable amino group.

As examples of coupling and diazo-components obtainable as describedabove, which contain a radical of the Formula 1, there may be mentioned(a) As diazo-components the secondary condensation products of 1 mol ofcyanuric chloride with 1 mol of methyl alcohol, isopropyl alcohol,methoxyethyl alcohol or an hydroxybenzene sulfonic acid and 1 mol of4:4'-diaminodiphenyl-3-sulfonic acid, 4 4'-diaminostilbene-2 2'-disulfonic acid, 4-(4"-aminobenzoyl-amino)-1-aminoben zene-Z-sulfonicacid, 1:3- or 1:4-diamino-benZene-l:4-diaminobenzene-Z-carboxylic acid,l:3-dianrinobenzene-4- sulfonic acid or 1:4-diaminobenzene-3-sulfonicacid, 2- methoxy-l:4-diaminobenzene-S-sulfonic acid and the secondarycondensation products of'the formulae i HN-- (b) As coupling componentsthe secondary condensation products of 1 mol of cyanuric chloride, 1 molof methyl alcohol, phenol or hydroxybenzene sulfonic acid and 1 mol of2-amino-S-hydroxy-naphthalene-6-su1fonic acid,Z-amino-5-hydroxynaphthalene-7-sulfonic acid or2-(4'-aminobenzoy1amino)-5-hydroxynaphthalene-7-sulfonic acid,1-acetoacetylamino-4-amino benzene-3-carboxylic acid or -3-sulfonicacid, 1-acetoacetylamino-4-aminostillbene-2:2'-disulfonic acid, 1-(3- or4-aminophenyl)-5- pyrazolone-B-carboxylic acid or 1 mol of the compoundof the formula S 0 H H0 8 NH1 COOH In making the dyestuifs of theinvention by condensing one of the aforesaid amino-azo-dyestuifs withcyanuric chloride and one of the aforesaid hydroxy-compounds in generalthe condensation may be carried out in either order ofsuccession, andthe condensations necessary for making the secondary condensationproducts to be used as. dyestuff components are advantageously carriedout by first making the dihalogen-triazine of the'Formula 3 andsubsequently condensing the latter with the dyestuff component necessaryfor the coupling.

Thec ondensations are advataneogusly carried out in the presence of anacid-binding agent, such as sodium acetate or sodium carbonate, in suchmanner that the resulting dyestuir' condensation product contains one ofthe three exchangeable halogen atoms of cyanuric chloride, for example,by working in a weakly acid or weakly alkaline to neutral medium and/orby maintaining the temperature as low as possible.

Without losing their valuable properties the dyestuffs of this inventioncan be isolated and worked up into useful dry dyestufi preparations. Thedyestuflis are isolated preferably at as low a temperature as possibleby salting out and filtration. After being filtered off the dyestulfsmay be dried, if desired, after the addition of extenders or buflers,for example, a mixturev of equal parts of a monoalkali phosphate and adialkali phosphate. The drying is preferably carried out at not too higha temperature and under reduced pressure. In certain cases itispossible-by spray drying the whole mixture resulting from the dyestufimanufacture to produce dry preparations directly, that is to say,without intermediate isolation of the dyestulf.

The new dyestufis of this invention are suitable for dveimr or nrinfinoavent mu'fln var-inf" a Mm-:01.

pecially cellulosic materials having a fibrous structure, such as linen,cellulose, regenerated cellulose and above all cotton. They areespecially suitable for dyeing by the so-called padding dyeing process,in which the goods are impregnated with an aqueous dyestuff solutionwhich may contain a high concentration of salt, and the dyestufi isfixed by treatment with alkali, advantageously at a raised temperature.

When the dyestuffs contain groups capable of forming complexes, forexample, an ortho:ortho-dihydroxy-azogrouping or anortho-hydroxy-carboxy-grouping such as is present in salicylic acidesters, the dyeings produced with such dyestuifs may be treated with anagent yielding metal, for example, an agent yielding chromium, butpreferably one yielding copper. The treatment with the agent yieldingmetal may be carried out in the usual manner. In many cases veryvaluable dyeings are obtained by using the process in which a dyeingproduced with the metal-free dyestufi is after-treated with an aqueoussolution which contains a water-soluble, preferably complex, coppercompound and a basic condensation product of formaldehyde with acompound which contains at least once the atomic grouping or a compound,such as cyanamide, that is easily convertible into a compound containingthe said grouping.

Dyeings produced with the new dyestuff preparations on cellulosic fibersare generally distinguished by the purity of their tints, by their goodfastness to light and 8 Example 1 18.4 parts of cyanuric chloride aredissolved in 400 parts by volume of methanol at 20-25 C. and thesolution is cooled to C. Then 2 parts of water are added and 9.3 partsof finely powdered sodium carbonate are strewn in.

The whole is stirred for 2 hours at 05 C., the temperature is allowed torise to 2025 C., and the whole is further stirred for 2 hours at thattemperature. It is then cooled to 5 C. and a solution of 18.8 parts of1:3- diaminobenzenel-sulfonic acid (in the form of its sodium salt) in700 parts by volume of water is added. A further 200 parts by volume ofa 4 N-solution of sodium acetate is added and the whole is stirred for 3hours at 30-35 C. The dissolved reaction product is precipitated by theaddition of hydrochloric acid and by volume of sodium chloride, andfiltered oii.

31.5 parts of the condensation product so obtained are stirred in 300parts of water, 300 parts of ice and parts of hydrochloric acid of 30percent strength, and

diazotization is carried out at ()-2 C. with parts b-yv volume of a 4N-solution of sodium nitrite. To the diam-suspension so obtained, whichis still acid to Congo, are added 15 parts of sodium bicarbonate, andthen the mixture is added to a solution, cooled to 0-2" G, of 42.3 partsof 1-benzoylamino-8hydroxynaphthalene-3:6- disulfonic acid (as thealkali salt) in 400 parts of water and 15 parts of calcined sodiumcarbonate. When the coupling is finished, the dyestufi is precipitatedby the addition of potassium chloride, filtered off, washed withpotassium chloride solution, and dried at 70 C. in vacuo. It dissolvesin cold water with a bluish red coloration, and dyes cellulose fibersfast bluish red tints by the padding dyeing process.

There are also obtained by this method by coupling the secondarycondensation products given in column I of the following table with thecoupling components given in column II similar dyestuffs, which dyecotton by the padding dyeing process the wet fast tints given in columnIII.

I II III N HO NH@ 0 CH3 1 H O-C CNH S0311 bluish red. N N

O HOgS- S0 11 ('11 N' 01 HO 1 2 H O OC C-NH SO3H greenish C N -S 0 Hyellow. NE 210 o a $1 $1 C=N N HO 3 113C O-C C-NH SOaH C- SO3H D0.

1 N N HG CI O=N C1 lH;

N HO NH-C 0 CH3 4 H3O O-(|3 (|.]iNH SOQH red.

N N I ('3 H0 8- Cl.

11 il Example 2 30.3 parts of 2-aminonaphthalene-4:8-disulfonic acid arediazotized in the presence of hydrochloric acid with 6.9 parts of sodiumnitrite. The diazo-cornpound is coupled in acetic acid solution with 15parts of l-amino- 3-acetyl-aminobenzene. The monoazo-dyestuff so formedis salted out, filtered off, and dissolved in 2000 parts of Water. Thesolution, after being neutralized With sodium carbonate, is run into anice-cold suspension of 18.4 parts of cyanuric chloride, and the whole isstirred for 30 minutes at to C. Then about 50 parts by volume of a 2N-solution of sodium carbonate are added dropwise so that the reactionmixture is maintained at a slightly acid reaction (pH value of 5.5 to6). When free amino groups can no longer be detected, an aqueoussolution of 9.4 parts of phenol and sufficient sodium carbonate toproduce a pH value of 8.5 to 9 are added, and the whole is stirred for afew hours at room temperature, the reaction mixture being maintainedweakly alkaline by the addition of further sodium carbonate. Thedyestuif so formed is then salted out, filtered off, and dried in vacuoat a moderately raised temperature. It dyes cotton from baths having ahigh salt concentration and in the presence of alkali, or by the paddingdyeing process, yellow tints that are very fast to light and Washing.

Similar dyestuffs are obtained by using 10.8 parts of orthoorpara-cresol, instead of 9.4 parts of phenol.

Example 3 24.1 parts of 2-phenoxy4:6-dichloro-1:315-triazine are asuspended in 1000 parts of water, and a neutralized solution of 18.4parts of 1:4-diaminobenzene-Z-sulfonic acid is added. About 50 parts byvolume of a 2 N-solution of sodium carbonate are gradually added, andthe whole is stirred for a few hours at 3040 C. The secondarycondensation product so obtained is separated by the addition ofhydrochloric acid and sodium chloride.

The product so obtained is diazotized in the usual manner With sodiumnitrite in hydrochloric acid solution and the diazo-compound is coupledin acetic acid solution with 29.3 parts of2-amino-8-hydroxy-naphthalene-6-sulfonic acid. The dyestuff so obtaineddyes cotton fast bluish red tints.

Similar dyestuffs are obtained by using 2-methoxy-4z6- dichloro 1:3:5triazine and 1:3-diaminobenzene-4-sulfonic acid instead of the indicated2-phenoxy-2z4-dichloro- 1:3:5-triazine and of the1:4-diaminobenzene2-sulfonic acid mentioned in this example.

Example 4 62.7 parts of the dyestuff of the formula so r! no (I31 0 NH--N=N s N N CO H l l HO3S NHO OCl CH are suspended in 2000 parts of waterand an aqueous solution of 9.4 parts of phenol is added. Such a quantityof an aqueous solution of sodium carbonate is then added dropwise in thecourse of 4 hours that the pH value of the reaction mixture ismaintained between 8 and 9. The dyestuff so formed is then salted outand filtered off. It dyes cotton by the padding dyeing process fastscarlet red tints.

A very easily soluble dyestuif having otherwise similar properties isobtained by using for forming the dyestuff 19.8 parts of sodium3-hydroxybenzene-l-sulfonate, instead of 9.4 parts of phenol.

Example 5 60.7 parts of the amino-azo-dyestuff (obtained by couplingdiazotized 4-amino-1: 1'-azobenzene-3 :4-disulfonic acid with2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid in the presence ofsodium carbonate followed by splitting off of the acetyl group by meansof a Warm dilute solution of sodium hydroxide) are dissolved in 2000parts of water. The resulting solution is run into an icecold suspensionof 18.4 parts of cyanuric chloride. The whole is stirred for one hour at05 C., and then a solution of 10% strength of sodium carbonate is addeddropwise until the reaction is neutral. When free amino groups can nolonger be detected 9.4 parts of phenol and such a quantity of sodiumcarbonate are added that the mixture is maintained at a pH value of 8 to8.5. After stirring the mixture for 4 to 6 hours at 40 C. the dyestuffformed is salted out, filtered OE, and dried in vacuo. It dissolves inwater with a red coloration, and dyes cotton by the padding dyeingprocess in the presence of alkali very pure red tints.

Example 6 2 parts of the dyestutf obtained as described in the first andsecond paragraphs of Example 1 are dissolved in 100 parts of water byboiling. A cotton fabric is impregnated at C. with the solution, andsqueezed to remove the excess of solution until the increase in theweight of the fabric is 70 percent. The fabric is dried, and then passedthrough a solution of 10 parts of sodium hydroxide and 300 parts ofsodium chloride in 1000 parts of cold water, squeezed until its increasein weight is 70% steamed for 60 seconds, rinsed, neutralized in asolution of 0.5 percent strength of bicarbonate, rinsed, soaped for 15minutes in a boiling solution of 0.3 percent strength of an ion-freedetergent, rinsed and dried. There is obtained a red dyeing which isfast to washing and light.

Similar results are obtained by using 20 or 30 parts of sodiumcarbonate, instead of 10 parts of sodium hydroxide, and steaming for 3minutes instead of 60 seconds.

Example 7 2 parts of the dyestuif obtained as described in the first andsecond paragraphs of Example 1 are dissolved in parts of water by theaddition of 1 part of sodium hydroxide. A cotton fabric is impregnatedwith the solution at room temperature, then squeezed until its increasein weight is 70%, and dried. The fabric is then steamed for seconds,rinsed, and finished in the manner described in Example 6. There isobtained a red dyeing that is fast to washing and light.

Example 8 2 parts of the dyestuff obtained as described in the firstparagraph of Example 4 are dissolved in 4000 parts of water. To thesolution are added 40 parts of trisodium phosphate and 80 parts ofsodium chloride, and 100 parts of a Well wetted cotton fabric areentered into the dyebath. In 45 minutes the temperature is raised to 90C., a further 80 parts of sodium chloride being added to the dyebathafter 30 minutes. The temperature is maintained at 90 C. for 30 minutes,and the dyeing so produced is rinsed and soaped for 15 minutes in aboiling solution of 0.3% strength of an ion-free detergent, rinsedagain, and dried. There is obtained a scarlet red dyeing that is fast towashing.

What is claimed is:

1. A water soluble azodyestufi which contains at least two sulfonic acidgroups imparting solubility in water and corresponds in its free acidstate to the formula wherein halogen represents a member selected fromthe group consisting of chlorine and bromine, n is a positive wholenumber up to 2, R represents a benzene radical, R is a member selectedfrom the group consisting of 13 m benzene and naphthalene radicals, Arepresents the radical of a coupling component containing a sulfonicacid group, and Y represents a member selected from the group consistmgof the lower alkoxy and phenoxy groups.

I I I I I I I least two suli'onrc acid groups imparting solubility 111water and corresponds in its free acid state to the formula Y-o-t l(l3-NHRN=NA in which Y represents a member selected from the groupconsisting of lower alkyl and phenyl groups, A represents the radical ofa coupling component which contains a sulfonic acid group and Rrepresents a radical of the benzene series containing a sulfonic acidgroup.

3. A monoazo dyestuff which contains at least two sulfonic acid groupsimparting solubility in water and corresponds in its free acid state tothe formula wherein Y represents a lower alkyl group and A represents amember selected from the group consisting of aminonaphthol sulfonic acidradicals and S-pyrazolone radicals containing a sulfonic acid group andbound to the azo linkage in 4-position.

4. A monoazo dyestufi which contains at least two sulfonic acid groupsimparting solubility in water and corresponds in its free acid state tothe formula wherein R represents the radical of naphthalene-sulfonicacid, A the radical of a hydroxynaphthalene sulfonic acid and Yrepresents a lower alkyl group.

6. The monoazo dyestufi which in its free acid state corresponds to theformula 7. The monoazo dyestuir which in its free acid state correspondsto the formula 8. The monoazo dyestuif which in its free acid statecorresponds to the formula H O NHO O 9. The monoazo dyestuff which inits free acid state corresponds to the formula 10. The monoazo dyestuifwhich in its free acid state corresponds to the formula References Citedin the file of this patent UNITED STATES PATENTS 2,795,576 Fasciati June11, 1957 UNITED STATES PATENT OFFICE Certificate of Correction PatentNo. 2,891,941 June 23, 1959 Alfred F asciati et a1.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction and that the saidLetters Patent should read as corrected below.

Column 1, line 47, for and read -a; column 2, line 50, for1-acetocetylamin0- read -1-acetoacetylamino-; line 51, foracetacetylamino read acetoacetylamino; column 5, line 57, for 1:4-diamino-benzene-1z read 1:4-diamino-ben zene,1:; column 6, line 52,for Theo ondensations are advataneogusly read The condensations areadvantageously-; columns 7 and 8, in the table, second column, under theheading I, opposite 2 the right-hand portion of the formula shouldappear as shown below instead of as in the patent:

NH: columns 9 and 10, in the table, second column, under the heading Iopposite 7 for that portion of the formula reading H CO read H CO-;column 14, approximately line 53, for that portion of the formulareading NO sread Signed and sealed this 22nd day of December 1959.

Attest: KARL H. AXLINE, ROBERT C. WATSON, Attestz'ng Ofioer.Gonwm'ssz'oner of Patents.

1. A WATER SOLUBLE AZODYESTUFF WHICH CONTAINS AT LEAST TWO SULFONIC ACIDGROUPS IMPARTING SOLUBILITY IN WATER AND CORRESPONDS IN ITS FREE ACIDSTATE TO THE FORMULA